Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-liquid crystalline polyester and method for forming same

ABSTRACT

Multilayer laminates including films, sheets, preforms, containers and other articles having at least one wholly aromatic, amorphous, stretchable liquid crystalline polymer layer with at least one non-liquid crystalline thermoplastic polyester layer are provided as well as methods for producing and stretching the multilayer articles. The laminates are suitable for thermoforming and stretch blow molding applications and may be stretched to at least 100 percent elongation at temperatures below 200° C. and at high total draw ratios without fractures or tears. Containers suitable for food or beverage products may be produced from the laminates.

FIELD OF THE INVENTION

This invention relates to multilayer laminates, including films, sheets,preforms, containers and other articles, comprising at least one layerof a wholly aromatic, amorphous, stretchable liquid crystalline polymerwith at least one non-liquid crystalline polyester layer, and methods ofproducing and stretching such liquid crystalline polymers and suchmultilayer articles. The disclosures in this application are related tothose in copending patent applications, Ser. Nos. 08/954,377,08/954,378, 08/954,997 and 08/955,000, filed Oct. 20, 1997.

BACKGROUND OF THE INVENTION

Multilayer laminates, containers and other articles have numerousapplications in industry, particularly for packaging applications.Kirk - Othmer Encyclopedia of Chemical Technology, Third edition, Volume10, page 216 (1980), Wiley-lnterscience Publication, John Wiley & Sons,New York, details generally the materials and processes required formaking such articles as well as their applications. Another article ofinterest, for example, is “Films, Multilayer,” by W. Schrenk and E.Veazey, Encyclopedia of Polymer Science and Engineering, Vol. 7, 106(1980). Generally, such articles are prepared by coprocessing individualpolymers in injection or extrusion operations or by laminatingindividually formed layers together or by a combination of theseprocesses. Coprocessing as discussed herein refers to forming and/orsubsequently processing at least two layers of polymeric material, eachlayer comprising a different polymeric material. Common polymers used inthese applications include polyethylene, polypropylene, ethylene-vinylacetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methylacrylate copolymer, polyvinyl chloride, polyvinylidene chloride,polyamide, polyester, polycarbonate, polystyrene, acrylonitrilecopolymers and the like. Desired properties in the laminates, films,sheets and the like, depend on the intended applications but generallyinclude good mechanical properties such as tensile and impact strengths,processability, tear resistance, gas barrier properties, moisturebarrier properties, optical properties, thermal and dimensionalstability and the like.

U.S. Pat. No. 5,256,351 to Lustig et al and U.S. Pat. No. 5,283,128 toWilhoit disclose biaxially stretched thermoplastic films frompolyethylene and a process to prepare them. U.S. Pat. No. 5,460,861 toVicik et al also teaches improved multilayer films from polyolefins.U.S. Pat. No. 4,911,963 to Lustig et at discloses an oriented multilayerfilm from nylon. U.S. Pat. No. 5,004,647 to Shah describes a coextrudedmultilayer film comprising ethylene-vinyl alcohol copolymer.

Many methods of forming useful articles from combinations of polymersrequire that all components of the combination be stretched, expanded orextended in one or more directions, or deformed in some other way, suchas by folding, creasing and the like. This stretching, extending orother deformation may be carried out concurrently with the process offorming the laminate or individual layers from the melt or may be partof a subsequent forming operation. Deformation can also be a requirementof using the article. Such methods of forming include but are notlimited to, uniaxial and biaxially stretching of extruded films,thermoforming of multilayer laminates, blowing of extruded orinjection-molded tubes, stretch blow molding of preforms or parisons,creasing or folding of laminates to form boxes, twisting of films toform a wrapper and the like.

Combining layers of different polymers is a method generally used toform a multilayer laminate which takes advantage of the differentproperties which may be available in the different polymer layers whilealso minimizing the amount of the more expensive polymer used.

Many methods of container formation require the collapse of a tube orthe folding of a multi-layer structure. In such cases, it is desirableto avoid wrinkles, to ensure that the various layers remain bonded toeach other and to avoid fracturing or tearing one of the layers. Othermethods of container formation require uniform stretching or expansionof the multilayer laminate at temperatures sufficient to stretch anypolymeric material present in the laminate. It is advantageous to beable to coprocess the laminate, for example, to fold, stretch, expand orcompress it without fracturing, tearing or otherwise destroying theintegrity of any layer.

Thermotropic liquid crystal polymers are polymers which are liquidcrystalline (i.e., anisotropic) in the melt phase. Other terms, such as“liquid crystal”, “liquid crystalline” and “anisotropic” have been usedto describe such polymers. These polymers are thought to possess aparallel ordering of their molecular chains. The state in which themolecules are so ordered is often referred to as either the liquidcrystal state or the nematic phase of the liquid crystalline material.These polymers are prepared from monomers which are generally long, flatand fairly rigid along the long axis of the molecule.

Generally, liquid crystal polymers (“LCPs”) have properties that arevery desirable, such as excellent chemical resistance, high mechanicalstrength, and excellent gas, moisture and aroma barrier properties. Itcan be, however, difficult to heat-bond articles made of LCPs togetheror to other materials. It also may be difficult to write or print onarticles made from LCPs.

LCPs are more expensive than conventional polyesters. Additionallyseveral conventional LCPs even in the form of thin films do not possesshigh optical clarity. In general LCPs cannot be stretched or deformedmore than a few percent unless they are heated to a processingtemperature range of from about 200° C. to about 320° C., preferablyfrom about 220° C. to about 300° C. Generally film and bottle formationprocesses require an excess of 100% elongation. For amorphous LCPshaving no measurable melting point, this processing temperature range isreferred to as the “molten state”. In addition, in this temperaturerange where conventional LCPs can be deformed, they have very low meltstrength and are weak. Tubes from conventional LCPs cannot be collapsedwithout wrinkling. Films or laminates containing one or moreconventional LCP layers are difficult to fold without delamination andsplitting. Preforms or parisons containing conventional LCP layers willhave fractures or tears in the LCP layer unless they are heated to orare in the molten state before stretching, which may be far too high atemperature for coprocessing the other layers in the laminate.

U.S. Pat. No. 4,384,016 to Ide et at discloses that when polymers whichexhibit anisotropic properties in the melt phase (i.e., thermotropicliquid crystal polymers) are extruded through a slit die and drawn inthe melt phase, films and sheets which exhibit high machine directionproperties are obtained. However, Ide et at recognizes that such filmsor sheets possess poor transverse directional properties which may limittheir usefulness in certain structural applications and proposeslaminating uniaxially oriented sheets at angles to one another toprovide a multiaxially oriented sheet.

Stretching or drawing of the laminated, multiaxially oriented sheetproposed by Ide et al is not disclosed.

Another method for producing a multiaxially oriented liquid crystalpolymer film is proposed by Harvey et at in U.S. Pat. No. 5,288,529wherein axially flowing liquid crystal polymer material is subjected totransverse directional forces to strain the axial flow, and then themicroscale structural orientation obtained is solidified to achieve aliquid crystal polymer film with nearly isotropic mechanical properties.Harvey et at proposes a process of shear orientation during extrusion toovercome the deficiencies in the mechanical properties of liquid crystalpolymer films, which films are disclosed as being inadequate for certainapplications because they can not be blown and drawn after extrusion ascoil polymers (such as polyethylene terephthalate) can. Morespecifically, it is disclosed that liquid crystal polymer films whichcomprise relatively straight, or fibrillar, molecules become highlyoriented in the die in the direction of extrusion and the flowing liquidcrystal polymer becomes anisotropic, more so than ordinary coil polymerswhich tend to randomize. Because the liquid crystal polymer becomeshighly oriented in the die anisotropically, it is disclosed that it maynot be possible to stretch the polymer substantially in the directiontransverse to its fibrillar orientation.

U.S. Pat. No. 5,534,209 to Moriya discloses that many of the physicalproperties of liquid crystal polymers are very sensitive to thedirection of orientation of the liquid crystal regions in the polymer.This may be very desirable for linear products such as filaments andfibers, but anisotropic properties are often undesirable in productshaving a planar forms, such as tape, films, sheets and the like. Moriyaalso discloses that shear orientation processes such as those disclosedin Harvey et al have a drawback in that they are unable to make thinmultiaxially oriented films without the formation of pinholes, tears andother imperfections. Moriya states that in the case of melt-processedthermotropic liquid crystal polymers which have very high processingviscosity, it is difficult to obtain films with uniform surfacesmoothness and thickness by shear orientation processes. This furtherincreases the film's tear sensitivity as well as its susceptibility tocurling and streaking.

Moriya obtains a liquid crystal polymer film having random orientationby feeding a thermotropic liquid crystal polymer into a melt regionformed in the nip between opposed inward facing surfaces of two supportmembranes. The randomly oriented liquid crystal polymer film formed bythe Moriya process may be multiaxially oriented by stretching thesandwich structure formed by the liquid crystal film and the two supportmembranes at or above the melting point of the liquid crystal polymer.

U.S. Pat. Nos. 5,364,669 and 5,405,565 to Sumida et al both disclosecomposite films comprising a layer of liquid crystal polymer having gasbarrier properties, an adhesive layer, and a thermoplastic layer formedfrom thermoplastics such as polyalkylene terephthalates, olefinpolymers, nylons, polycarbonates and the like. The composite films aresuitable as a food packaging material. Sumida et al discloses thatmolten liquid crystal polymer may be biaxially stretched from the meltbut should be extruded downward from the die to prevent the problemsassociated with low melt viscosity and weakness of the melted film whichcreate difficulties when the molten liquid crystal polymer film isextruded upward from the die. Examples of the Sumida et al process areprovided wherein Vectra® A900 (a trademark of Hoechst CelaneseCorporation of Somerville, N.J.) wholly aromatic liquid crystalpolyester resin is extruded at 290° C. at a blow ratio of 5.5 and adraft ratio of 6.0 to obtain a multiaxially oriented liquid crystalpolymer film. Blow molding and stretch blow molding to obtain bottles orjars are not disclosed.

It is often desirable to obtain shaped articles from multilayerlaminates by thermoforming and/or blow molding processes because theyare cost effective methods of making mass produced shaped articles.However, such processes often are either not practical or not possiblewith materials that must be melt stretched, such as the wholly aromaticVectra® liquid crystalline resins and other melt-processable liquidcrystalline polymers utilized in the processes described above. Thus, itwould be desirable to have a stretchable liquid crystalline polymerwhich may be stretched not only when in the molten state, but also attemperatures above the T_(g) of the liquid crystalline polymer but belowthe molten state, or stretchable below about 200° C. Furthermore, itwould also be desirable to have laminates and articles formed from suchlaminates comprising a layer of such a stretchable liquid crystallinepolymer layer.

Often, copolymers or blends of different constituent polymeric materialsare used to provide a combination of properties in the resultingcopolymer or blend that none of the individual constituent polymericmaterials possess by themselves. For example, it might be proposed tocombine a melt-processable liquid crystalline material having excellentmechanical and gas barrier properties together with a thermoplasticpolymeric material in an attempt to obtain a blend or copolymer havinggas barrier properties, good mechanical properties and stretchability atlower temperatures.

However, it has been recognized that such combinations, prepared eitheras copolymers or blends, may exhibit what is termed a “negativesynergistic effect”. That is, even if the polymers are compatible incombination and form a copolymer or blend, the combination of polymersmay have less desirable properties than would have been predicted. Theexact mechanism for this effect is not fully understood, but often theproperties in the copolymer or blend are closer to a combination of theleast desirable properties of each individual constituent polymer,rather than the best properties of each. Even when good properties areobtained, the resultant polymeric material may have certainshortcomings.

U.S. Pat. No. 5,326,848 to Kashimura et al discloses thermotropic liquidcrystal polyesters produced by a hybrid copolymerization process whereinpolyesters such as polyethylene terephthalate (PET), polyethylenenaphthalate (PEN), or copolymers of PET and PEN are combined withconventional liquid crystal polyester structural units based on hydroxynaphthoic acid and hydroxy benzoic acid, or units based on hydroxynaphthoic acid alone. Kashimura et al proposes to achieve both excellentformability and gas barrier properties and discloses laminates havinglayers of the liquid crystal polyester compositions with layers of otherpolymers such as polyesters, polyolefins and polyamides to producelaminated containers such as cups and bottles. A polyester compositioncapable of preparing formed shapes by deep drawing an unstretched sheetis disclosed as comprising PET combined with units based on hydroxynaphthoic acid and hydroxy benzoic acid. However, it is disclosed thatthe gas barrier property of this deep drawing composition may sometimesbe inferior to the gas barrier properties obtained by the othercompositions disclosed which are not disclosed as suitable for deepdrawing. In all of the liquid crystal polyester compositions disclosedby Kashimura et al, an aliphatic dihydroxy component must be present inat least 15 mol percent in the liquid crystalline polyester. Althoughthe formation of bottles and blow molding are disclosed, neither aredemonstrated, nor are draw ratios for bottle formation or blow moldingdisclosed. Biaxial stretching of a film of the composition heated to100° C. to 240° C. at a ratio of 3×3 is disclosed.

The processes disclosed by Kashimura et al for producing liquidcrystalline polyester compositions consist of reacting a polymer such asPET, PEN or copolymers of these polyesters together with monomers basedon hydroxy naphthoic acid and hydroxy benzoic acid or hydroxy naphthoicacid alone. This hybrid polymer/monomer copolymerization is necessitatedby the requirement that at least 15 mol percent of the liquidcrystalline polyester composition be an aliphatic dihydroxy component.This aliphatic component must be combined with the terephthalic acidand/or naphthalene dicarboxylic acid component before it is combinedwith the liquid crystal polyester monomeric moieties because it preventsthe formation of the desired hybrid polymer. The process disclosed byKashimura et al for producing such LCPs is highly variable and,therefore, difficult to develop into a full-scale commercial process toobtain liquid crystal polymer compositions in substantial quantities.

Stretchable multilayer laminates and articles comprising an LCP layerhave been proposed. For example, JP 5,177,797 A discloses thatmultilayer containers may be prepared from a laminate comprising layersof a thermoplastic resin and an LCP. Other disclosures of similar natureand of interest include, for example, JP 5,177,796 A; JP 1,199,841 A; JP5,169,605 A; and WO 9,627,492 A.

Pending application, Ser. No. 08/761,042, filed Dec. 5, 1996, discloseslaminates comprising an LCP layer in the middle and peelablethermoplastic layers on the outside. Pending patent application, Ser.No. 081761,109, filed Dec. 5,1996, discloses polarizer laminatescomprising dyed LCP layer in the middle and non-peelable thermoplasticlayers on the outside. Pending applications, Ser. Nos. 08/954,377,08/954,378, and 08/954,997 disclose adhesives for making multilayers atleast one of those layers being from an LCP.

It would be desirable to produce stretchable LCPs and also to producemultilayer laminates or articles having one or more LCP layers bonded toone or more non-LCP layers to obtain a multilayer structure having thebest properties of all of the various layers, such as a multilayerstructure having good gas barrier properties, mechanical properties,optical properties and relatively low cost. It would be desirable forsuch liquid crystalline polymers and multilayer structures to bestretchable not only at temperatures where the LCP composition is in themolten state, but also at lower temperatures, above the T_(g) of the LCPcomposition, but below the temperature range where the LCP compositionis in the molten state. It would be desirable to be able to stretch suchan LCP or LCP laminate more than once and achieve high draw ratios. Itwould be desirable to produce an LCP for such a laminate via apredictable, stable process, capable of use on a large commercial scale.

SUMMARY OF THE INVENTION

The present invention provides individual layers as well as multilayerlaminates comprising a wholly aromatic, amorphous, low-temperaturestretchable liquid crystalline polymer and a non-liquid crystallinethermoplastic polyester. The liquid crystalline polymer used in thepresent invention is described below and may be produced reproduciblyand economically in full-scale commercial processes from suitablemonomeric moieties and has excellent barrier properties. The liquidcrystal polymer or polymers used in the invention may be stretched notonly in their molten state, but also at temperatures greater than theT_(g) of the liquid crystalline polymer composition but less than about200° C. They may be stretched more than once, and may be stretched to atotal area draw ratio greater than 10, or more preferably greater than15 without fractures and/or tears.

The inventive laminates are useful to form multilayer films, sheets,preforms and parisons, and other articles with properties suitable forapplications in many fields including, for example, food, cosmetic,chemical and industrial packaging applications. The inventive multilayerlaminate exhibits no fractures and/or tears in any of layers of thelaminates even when stretched to total area draw ratio greater than 15.

The present invention also provides processes to prepare such laminates,including films, sheets, preforms or parisons, or other articles.

The present invention also provides useful articles from laminates ofthe liquid crystalline polymer composition together with non-liquidcrystalline thermoplastic polyesters.

DESCRIPTION OF THE INVENTION

Multilayer laminates including films, sheets, preforms, parisons,containers, and other similar articles (“articles” in general hereafter)have now been prepared from at least one layer of stretchable, whollyaromatic amorphous or “glassy” LCPs and at least one layer of non-liquidcrystalline polyester. Individual layers of the stretchable LCP usefulin the invention have also been prepared.

The multilayer laminates of the invention comprise at least one whollyaromatic, amorphous, stretchable liquid crystalline polymer layer and atleast one thermoplastic, non-liquid crystalline polyester layer. Theliquid crystalline polymer layer and laminates prepared from the liquidcrystalline polymer layer of the invention are stretchable attemperatures below a molten state of the liquid crystalline polymer(“LCP”). The liquid crystalline polymer layer is obtained from theliquid crystalline polymer described below. The LCP layer of theinvention is stretchable at temperatures below its molten state withoutthe need for adding substantial amounts of non-LCP thermoplasticpolymers, fillers or additives. However, there may be added amounts ofnon-LCP thermoplastic polymers, fillers or additives without adverselyaffecting the barrier or stretchability properties of either the LCPlayer or the laminate of the invention. Exemplary amounts are up toabout 10 mol percent total of added non-LCP thermoplastic polymers,fillers or additives, with the LCP suitable for the present inventioncomprising at least about 90 mol percent of the LCP layer. In otherembodiments of the invention, the liquid crystalline polymer layerconsists essentially of the liquid crystalline polymer. The liquidcrystalline polymer is wholly aromatic in that each of the monomericunits that the liquid crystalline polymer is derived from are monomerswhich have no aliphatic components, as described further below.

The liquid crystalline polymer is amorphous in that it exhibits a glasstransition temperature (T_(g)) but displays no melting point transition(T_(m)) under differential scanning calorimetry (DSC) analysis. Incontrast, semi-crystalline liquid crystalline polymers exhibit both aT_(g) and a T_(m) under DSC analysis.

The liquid crystalline polymer composition used in the present inventionhas a processing temperature range in which it can be described as beingin a molten state, that processing temperature range being from about200° C. to about 320° C., or more preferably from about 220° C. to about300° C. The liquid crystalline polymer compositions may be stretched notonly in the molten state, but at temperatures below the molten state andabove the T_(g) of the liquid crystalline polymer composition. In thepresent invention, the liquid crystalline polymer compositions arestretchable to total area draw ratios of at least about 10, morepreferably at least about 15, without the appearance of any fractures ortears in any layer of the laminate.

The liquid crystalline polymers used in the multilayer articlesdescribed herein are wholly aromatic polymers, with relatively linearstructures, which exhibit liquid crystalline behavior in the moltenphase. They include, but are not limited to, wholly aromatic amorphouspolyesters or wholly aromatic amorphous polyesteramides. In embodimentsof the invention, the liquid crystalline polymers preferably compriserepeat units which, as described in U.S. Pat. No. 5,672,296,incorporated herein by reference in its entirety, correspond to thegeneral formula:

-[P¹]_(m)- [P²]_(n)-[P³]_(q)-

wherein P¹ is an aromatic hydroxy carboxylic acid or an aromatic aminocarboxylic acid; P² is an aromatic dicarboxylic acid; P³ is a phenoliccompound; m, n and q represent mole percent of the respective monomersranging generally from 5 to 70 percent individually. The preferred rangeof m is about 5 to 40 percent, n is about 5 to 40 percent and q is about5 to 40 percent. In addition to P¹, P² and P³, additional monomericmoieties such as, for example, a second aromatic hydroxy carboxylic acidmoiety or an aromatic amino carboxylic acid moiety -[P⁴]_(r)- and adiphenol moiety -[P⁵]_(s) may be part of the polymer repeat unit, inwhich case r is about 5 to 20 mole percent, and s is about 5 to 20 molepercent. P⁴ is different from P¹ and P⁵ is different from P³. Stilladditional monomers may also be present such as, for example, phenylhydroquinone, methyl hydroquinone and the like. In the above generalformula, the monomers P¹ and P⁴ are selected from the group consistingof 4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-aminobenzoicacid, and 4-carboxy-4′-hydroxy-1,1′-biphenyl. 4-Hydroxybenzoic acid ispreferred. P² may be terephthalic acid, isophthalic acid, phthalic acid,2-phenylterephthalic acid, 1,2-naphthalenedicarboxylic acid,1,4-naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid and4,4′-biphenyldicarboxylic acid; terephthalic acid is preferred. P³ isselected from the group consisting of resorcinol, hydroquinone, methylhydroquinone, phenyl hydroquinone, catechol and 4,4′-dihydroxybiphenyl;4,4′-dihydroxybiphenyl is preferred. P⁵ is a diphenol selected fromresorcinol, hydroquinone, catechol, 4,4′-dihydroxybiphenyl andbisphenol-A.

In preferred embodiments of the invention, the liquid crystallinepolymer more preferably comprises a wholly aromatic thermotropic liquidcrystal polyester which comprises the following five monomeric units:4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, terephthalic acid,4,4′-dihydroxybiphenyl and resorcinol, in a molar ratio 30:30:20:10:10respectively (referred to as COTBPR hereafter). COTBPR is disclosed inU.S. Pat. No. 5,656,714 to Shen et al incorporated herein by referencein its entirety. Although particularly preferred, COTBPR is only one ofmany various wholly aromatic, amorphous, stretchable liquid crystallinepolyester compositions disclosed therein which may be suitable in thepractice of this invention. Shen et al also discloses semi-crystallinewholly aromatic liquid crystalline compositions which are not suitablein the practice of this invention. Examples of both amorphous andsemi-crystalline compositions are listed in Table I of theaforementioned U.S. Pat. No. 5,672,296.

The multilayer structures of this invention comprise at least one layerof the above-described wholly aromatic, amorphous, stretchable LCP. Theother layer or layers may comprise non-liquid crystalline polyesters. Asdiscussed above, thermotropic liquid crystalline polyesters are polymerswhich are liquid crystalline, (i.e., anisotropic) in the melt phase.Non-liquid crystalline polyesters are defined as polymers which are notliquid crystalline in the melt phase. In other words, they are isotropicin the melt phase. Examples of the non-liquid crystalline polyestersused for preparing the multilayer structures of the invention include,but are not limited to, polyethyleneterephthalate,polyethyleneisophthalate, polyethylene-2,6-naphthalate,polybutyleneterephthalate, polypropyleneterephthalate, copolyesterswhere the diacid component can be terephthalic acid and derivativesthereof, isophthalic acid and derivatives thereof, 1,2-, 1,3-, 1,4-,1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,4-, 2,5-, 2,6-, 2,7, 2,8-, isomers ofnaphthalene dicarboxylic acid and derivatives thereof, 4,4′-biphenyldicarboxylic acid and derivatives thereof, 4,4′-diphenyletherdicarboxylic acid and derivatives thereof, stilbenedicarboxylic acid andderivatives thereof, linear and mono and bis cyclic aliphaticdicarboxylic acids of 5-12 carbon atoms and derivatives thereof,copolyesters where the diol component can be a linear aliphatic diol of2-12 carbon atoms and derivatives thereof, 2-methyl-propanediol,2,2′-dimethylpropanediol, cyclohexanediol, cyclohexanedimethanol,1,3-bis(2-hydroxyethoxy)benzene and derivatives thereof,1,4-bis(2-hydroxyethoxy)benzene and derivatives thereof, bis(4-beta-hydroxyethoxyphenyl)sulfone and derivatives thereof, diethyleneglycol,poly(ethylene) glycol, poly(propylene) glycol, poly(tetramethylene)glycol, as well as structural units derived from polyhydric alcohol suchas glycerol trimethylolpropane triethylpropane or pentaerythritol(within an amount that melt processing of the polyester will not beaffected), blends of the above polyester and copolyester compositions,post consumer recycled PET as well as its mixtures. PET is preferred dueto its high availability. In the multilayer laminates of the invention,the non-liquid crystalline polyester may comprise monomeric residuesselected from the group consisting of terephthalic, isophthalic andnaphthalene dicarboxylic moieties, and mixtures thereof. The non-liquidcrystalline polyester may also comprise monomeric residues selected fromthe group consisting of ethylene glycol, propylene glycol and butyleneglycol moieties and mixtures thereof.

Laminates and other articles comprising the LCPs and non-polyesterthermoplastics such as polyolefins are also desirable and are thesubject of copending patent application, Ser. No. 08/955,000, filed Oct.20, 1997.

The liquid crystalline polymer layer and the multilayer laminates of thepresent invention have good stretchability in both the machine direction(“MD”) and the transverse direction (“TD”) at various temperatures. Theymay be stretched uniaxially in either direction, MD or TD, or biaxiallyeither sequentially or simultaneously, or stretched or expanded into amold. The laminates of the present invention have excellent mechanical,optical and barrier properties. Generally, an adhesive is not necessaryto bind the layers of the laminate. However, if one is desired,copending applications stated above and filed of even date herewithdescribe adhesives useful for such applications. Such an adhesive mayalso be coextruded as an additional layer in the same process.

In embodiments of the invention, several different processes may be usedto prepare the LCP layer of the invention or the multilayer laminates ofthe invention which may comprise two, three, four, five or more layers.The order of the individual layers in the laminate as well as the natureof the inner layers and outer layers in the laminate may be chosenaccording to the application desired and equipment used. Such variationsare well known to those skilled in the art. The laminate mayadditionally contain other optional layers such as, for example, a heatsealing layer, a FDA approved food contact layer, an adhesive layer, acolored layer, an ultraviolet blocking layer, an oxygen scavenging layerand a layer containing regrind or recycle materials. Such layers mayalso be coextruded in the same process described above or may besubsequently added separately. Additionally, one or more of the layers,including coextruded layers containing the LCP, may be extrusion coatedonto other layers, including, for example, aluminum foil, paperboard, orsteel.

In general, the process of forming a layer of the wholly aromatic,amorphous, low-temperature stretchable liquid crystalline polymer may beany suitable means of processing a thermotropic LCP. Such methods offorming a layer of the LCP include, but are not limited to, injectionmolding, extrusion, compression molding, or coating onto a substrate. Inpreferred embodiments of the invention a central layer of the LCP iscoextruded between two outer protective layers which are later removedto form a thin, smooth single layer of the LCP. Layers of LCP may beformed as thin as 0.5 mil by this method.

Processes of forming a laminate comprising at least one layer of the LCPuseful in the invention and at least one layer of non-liquid crystallinepolyester may be any suitable means for combining two or more layers ofthermoplastic polymer to form a laminate. Three general categories oflaminate forming methods are exemplary, but not exhaustive, of possiblemethods of laminate formation. The first category is combining twopolymer layers before they solidify, i.e., when they are both in themolten state. Extrusion methods such as feedblock coextrusion ormulti-manifold coextrusion are examples of such a method and are bothacceptable ways of forming the laminate according to the invention.Another category is combining an unsolidified, i.e., molten polymerlayer with a solidified polymer layer. Processes such as extrusioncoating and extrusion lamination are in this category and are suitablefor forming the laminates of the invention. Combining solidified layersis the third general laminate forming category and lamination andcertain coating processes are suitable for forming the laminate of theinvention in this manner.

In an exemplary process, an LCP suitable for the invention and asuitable non-liquid crystalline polyester are coextruded simultaneouslyin a conventional coextrusion process using a feedblock to combine thepolymer streams right at the die exit. The polymer streams join togetherwhile they are still above the melting point, resulting in a multilayerfilm exiting the die. The multilayer laminates of the present inventionmay also be extruded in planar, tubular, or other configurations. Also,a tubular laminate may be coextruded and slit or otherwise opened toform a planar coextrudate. The multilayer laminates of the presentinvention may be stretched during extrusion, subsequent to extrusion, orboth during and subsequent to extrusion. The tubular multilayer laminatemay also be formed from the multilayer laminates of the presentinvention by spiral winding. Other suitable processes such as, forexample, compression or injection molding, may also be used to producethe laminates of the present invention including films, sheets,preforms, parisons and other articles.

The multi-layer structures may be formed into articles by suitablemethods. The LCP layer and the LCP-containing multilayer laminates ofthe invention possess properties ideally suited for thermoforming, blowmolding and other methods of mass producing shaped articles with the useof heat and stretching. Such processes are well known to those skilledin the art. The various techniques by which film or sheet may be formedinto useful articles are described in such works as James L. Throne,“Thermoforming,” (Hanser Publishers, New York, 1987) which isincorporated herein by reference. Similarly, if the LCP-containinginventive laminates are coextruded in the form of a tube or parison,then these are ideally suited for blow molding. The various blow moldingtechniques, such as extrusion blow molding, injection blow molding,stretch blow molding, and the like, are described, for example, inDonald V. Rosato and Dominick V. Rosato, editors, “Blow MoldingHandbook,” (Hanser Publishers, 1988). Such parisons suitable for variousblow molding processes can also be produced by injection-molding or co-injection molding as is well-known to those skilled in the art. Inaddition, a container can be formed by a combination of these processes,for example, extruding a multi-layer parison containing a layer of theLCP, extrusion-blow- molding this parison to form a shaped insert,injection molding a polyester, such as polyethyleneterephthalate or thelike, around the outside of this insert to form a preform, and finallystretch-blow molding the preform to form a bottle, jar or othercontainer. Alternatively, the multi-layer insert can be produced bythermo-forming a planar sheet. These insert-molding processes aredescribed, for example, in U.S. Pat. No. 5,443,766 to Slat et al andU.S. Pat. No. 5,464,106 to Slat et al, the disclosures of which arehereby incorporated by reference in their entireties. Such stretch-blowncontainers are useful for a variety of packaging applications such asfor foods, beverages, cosmetics, chemicals and industrial products.

In the method of stretching the LCP layer or the multilayer laminatecomprising at least one layer of LCP according to the present invention,the LCP layer or the multilayer laminate comprising at least one whollyaromatic, amorphous, stretchable liquid crystalline polymer layer and atleast one thermoplastic, non-liquid crystalline polyester layer isformed. The multilayer laminate may be stretched at a temperature belowa molten state of the liquid crystalline polymer as well as at atemperature within the molten state of the liquid crystalline polymer.In the method according to the invention, the multilayer laminate may beheated, prior to stretching, to a temperature above the T_(g) and belowthe molten state of the liquid crystalline polymer. In the method of thepresent invention, the multilayer laminate may be stretched by variousthermoforming methods including, but not limited to, vacuum forming,plug assist thermoforming, compression molding and the like. Themultilayer laminate of the present invention may be formed bycoextruding the individual layers or by forming the layers separatelyand laminating them together, or by any other acceptable method offorming the laminate.

The multilayer laminate may be stretched by thermoforming into a shapehaving an innermost surface and an outermost surface. In addition, thethermoformed laminate may then be placed in a mold, and thermoplasticmaterial may be injected into the mold to form an outer layer in contactwith the outermost surface of the thermoformed laminate.

In other embodiments of the invention, the liquid crystalline polymerlayer and the non-liquid crystalline polyester layer may be formedeither individually or together by coating onto a substrate. The coatingmethod may be extrusion coating, dispersion coating, solvent coating, orany other acceptable coating method. The multilayer laminate may beapplied in coating form to a substrate such as paperboard, aluminum orsteel. The substrate may be subsequently stretched or deformed to form apackage, container, or other coated articles.

In other embodiments of the invention, the multilayer laminate of theinvention may be in the form of a stretchable multilayer preform forblow molding. The method of producing such a stretchable multilayerpreform for blow molding according to the invention comprises the stepsof forming a first layer having an inner surface, an outer surface, anopen end and an opposite end, and comprising a thermoplastic non-liquidcrystalline polyester. A second layer having an inner surface, an outersurface, an open end and an opposite end is also formed. The secondlayer comprises a wholly aromatic, amorphous, stretchable liquidcrystalline polymer. The preform is stretchable at a temperature below amolten state of the liquid crystalline polymer, and the inner surface ofone of the layers is in contact with the outer surface of the otherlayer, and the open ends and closed ends of both layers are coincident.The layers of the preform may be formed by extrusion or injectionmolding, or by any other suitable process for manufacturing themultilayer stretchable preform of the invention. The stretchablemultilayer preform of the invention may be expanded into a mold to forma container by methods such as blow molding, stretch blow molding,biaxial stretch blow molding, and the like.

Additionally, individual layers or multilayer laminates coextruded inthe form of a tube or a parison can be collapsed and sealed at one orboth ends to form a tube, a bag or a pouch. Optionally, one or moredispensing devices or orifices can be inserted. In addition, thecollapsing and folding can be carried out in such a way as to form aso-called stand-up pouch. Such formed articles are ideally suited forvarious packaging applications, including containers for food,beverages, cosmetics, chemicals, pesticides and automotive, or varioussolid articles requiring the protection afforded by such a package.Tubes, bags and pouches can also be formed from such planar multi-layerfilms by well-known techniques of seaming and sealing or spiral- windingand the like.

The films, sheets, laminates, cups, tubs, trays, pails, bottles, jars,bags, pouches, tubes and boxes and the like formed by the above methodsas well as others well-known to skilled artisans may, in some cases,possess a degree of transparency when compared with other known LCPs.Optionally, the articles can be made translucent or opaque, usingwell-known techniques, such as coatings, printing or pigmentation of oneor more layers and the like.

Useful containers can also be formed from multi-layer structuresobtained by extrusion-coating one or more polymeric layers, including atleast one layer of the LCP, onto another already formed substrate. Sucha substrate may be formed from one or more polymers, or from one or moremetallic layers or from cellulosic layers, such as paperboard, orcombinations of the foregoing. Such multi-layer structures can then beformed into containers by folding or otherwise deforming the structureand forming the appropriate seals to close the structure. Typicalcontainers formed by such processes include boxes or tubes of variousshapes and sizes and the like, which may optionally be equipped withsome type of opening device or dispensing orifice. Such containers arewidely used for various packaging applications, especially for theaseptic packaging of foods and beverages.

The polymers and processes described herein and used to form thelaminates of the present invention are not limiting in any way as to thethicknesses of the various layers in the laminates. Also, the individuallayers may have the same or different thicknesses; the equipment ischosen accordingly. Such methods are well known to the skilled artisan.

The multilayer laminates as well as the articles described hereinpossess excellent combination of mechanical, optical and thermalproperties, in addition to high barrier properties to oxygen andmoisture, as well as chemical resistance and the ability to be printedor decorated, to make them ideally suitable for applications as, forexample, food and beverage containers, cosmetics packages, drugpackages, solvent storage containers, chemical containers, gas tanks andthe like or for packaging a variety of consumer and industrial products.The amorphous, wholly aromatic, stretchable LCPs can be used in suchthicknesses within the given article of the present invention to becost-effective even though they may themselves have a somewhat higherinitial cost.

The following Examples are provided in order to further illustrate theinvention. The scope of the invention, however, is not to be consideredlimited in any way thereby.

EXAMPLES Example 1

Coextrusion of Multilayer Film Comprising Three Layers:

PET resin available under the brand name designation “T80” bottle resinavailable from Hoechst Trevira, a Hoechst group company, Charlotte,N.C., was fed into a 3.5 inch diameter, single screw extruder and exitedthe extruder at final melt temperature of 270° C. At the same time, awholly aromatic, amorphous, thermotropic liquid crystalline polyestercomprising the following five monomeric units: 4-hydroxybenzoic acid,6-hydroxy-2-naphthoic acid, terephthalic acid, 4,4′-dihydroxybiphenyland resorcinol, in a molar ratio 30:30:20:10:10, respectively (COTBPR)was fed into a single screw extruder having a two inch diameter screwand exited the extruder at a final melt temperature of 285° C. Both meltstreams were fed to a Cloeren five-layer MBM combining block supplied byCloeren of Orange, Texas. The Cloeren combining block was mounted on anEDI single slit die (from Extrusion Die Incorporated, Chippewa Falls,Wis.). The molten polymer streams were delivered to the feed block wherethe polymer flows were divided, the PET flow being divided into the Achannels of the feed block, and the LCP flow being fed into the Bchannel of the feed block. The streams were combined so that theyemerged from the die lips as a multilayer laminate. The resultantmultilayer laminate structure impinged on a chill roll and was taken upon a roll winder. During the extrusion process, the overall thickness ofthe extruded film was continuously monitored by a beta gauge locatedafter the chill roll. A multilayer film having the following three layerstructure (from top to bottom) was produced: PET, 6.5 mil/COTBPR, 3mil/PET, 6.5 mil.

Example 2

Uniaxial and Biaxial Stretching Experiments:

Seven samples of the PET/COTBPR/PET coextruded film described in Example1 were also stretched both uniaxially and biaxially on a BrucknerStretching Frame Model Karo II (from Bruckner Maschinenbau, Tittmoning,Germany) having gripping means, infrared heating means, and dual digitaldrives. The stretching frame received 6″ transverse direction (TD) by 6″machine direction (MD) samples. The film samples were heated by aninfrared heating system. The film surface temperature was measured by aninfrared pyrometer and drawing was initiated when the film reached theset drawing temperature indicated in Table I. Table I summarizes theresults of these drawing trials. In Table I, draw ratio is the ratio offilm length after stretching to the initial length. When the film wasstretched biaxially, the overall draw ratio was the product of TD and MDlinear draw ratios. The above-described PET/COTBPR/PET coextruded filmsshowed good drawability both uniaxially and biaxially (both in themachine direction (MD) and transverse direction (TD)) at varioustemperatures. For example, by uniaxial stretching at 145° C., a drawratio of 5×1 in the machine direction was achieved and with 3×3 biaxialstretching at 135° C. and 145° C. a total draw ratio of 9 was achieved.Layer to layer thickness uniformity for the layers was good as wastransparency and general aesthetics. The films showed good layer tolayer adhesion. Orientation on a molecular level was confirmed byperforming wide angle x-ray diffraction measurements on the uniaxiallydrawn films. Oxygen transmission measurements were performed at 23° C.according to both ASTM 3985 and DIN 53380 Part 3, using an OxTran 100instrument from Modern Controls Incorporated, North Minneapolis, Minn.

TABLE I Drawing Oxygen Temp. Draw Ratio Overall Transmission Run # [C.]TD MD Draw Ratio Rate* 1 125 3 2 6 0.195 2 135 3 2 6 0.218 3 135 3 3 90.211 4 145 3 3 9 0.287 5 145 1 3 3 6 145 1 4 4 7 145 1 5 5 *units in:cc/100 sq inch day atm

Example 3

Uniaxial Stretching of Multilayer Films:

The same Bruckner stretching unit from Example 2 was used to uniaxiallystretch samples prepared from the same stretchable COTBPR used inExample 1. The COTBPR layer was the central layer in a multilayerlaminate structure having 10 mil layers of polyethyleneterephthalate-isophthalate copolymer comprising 17.5 weight percentisophthalic acid units and the balance of the dicarboxylic acid unitsbeing terephthalic acid on either side of the COTBPR layer. This 17.5weight percent isophthalic acid copolymer (hereinafter designated“PETIP”) was extruded together with the COTBPR in the same manner andwith the same equipment as described in Example 1. Two differentthicknesses of COTBPR were used as central layers, 1 mil and 5 mil,resulting in two different multilayer laminates. The first multilayerlaminate comprised: 10 mil PETIP/1 mil COTBPR/10 mil PETIP, the secondmultilayer laminate comprised: 10 mil PETIP/5 mil COTBPR/10 mil PETIP.The two different laminates were stretched at three different drawtemperatures at a 2.5 draw ratio in the extrusion machine direction(MD). The transverse direction was held at a constant width. The sampleswere heated with infrared heaters and the film surface temperature wasmonitored by an infrared pyrometer. When the desired draw temperaturewas reached as indicated in Table II, the drawing sequence was initiatedwith a draw speed of 1.25 inches per second. Layer to layer thicknessuniformity for the layers was good with no fractures in the COTBPR layerobserved. Full uniform stretching, i.e., homogeneously decreasing theoriginal thickness of the LCP layer across the entire expanse of thestretched laminate, was achieved in all of the samples.

TABLE II COTBPR Layer Thickness Drawing Draw Ratio Run # [mil] Temp. [°C.] TD MD Comments 1 1 125 1 2.5 Full uniform stretching 2 5 125 1 2.5Full uniform stretching 3 1 135 1 2.5 Full uniform stretching 4 5 135 12.5 Full uniform stretching 5 1 145 1 2.5 Full uniform stretching 6 5145 1 2.5 Full uniform stretching

Comparative Example:

Uniaxial Stretching of Multilayer Films:

The Bruckner same stretching unit from Example 2 was used to uniaxiallystretch samples of a 2 mil Vectran® FA film within a multilayerstructure having a 10 mil PETIP layer as in Example 3 on either side ofthe Vectran® FA film. Vectran® FA is a film produced from Vectra® A950wholly aromatic LCP resin (available from Hoechst Ticona, a Hoechstgroup company, Summit, N.J.). The multilayer laminate was produced onthe same equipment and in the same manner as Example 1. Four drawtemperatures at a 2.5 draw ratio in the extrusion machine direction wereused. The transverse direction was held at constant width. The sampleswere heated with infrared heaters and the film surface temperature wasmonitored by an infrared pyrometer. When the desired draw temperature asindicated in Table III was reached, the drawing sequence was initiatedwith a draw speed of 1.25″/sec. At all drawing temperatures up to 175°C. the Vectran@ layer fractured as soon as drawing was initiated. Higherdrawing temperatures could not be achieved because the PETIP layersbegan to melt.

TABLE III COTBPR Layer Thickness Drawing Draw Ratio Run # [mil] Temp. [°C.] TD MD Comments 1 1 125 1 2.5 Brittle Break of Vectran ™ layer withno stretching possible 2 2 135 1 2.5 Brittle Break of Vectran ™ layerwith no stretching possible 3 2 145 1 2.5 Brittle Break of Vectran ™layer with no stretching possible 4 2 175 1 2.5 Brittle Break ofVectran ™ layer with no stretching possible

Example 4

Stretch Blow Molding Multilayer Bottles:

A three-step process was used to form a 12 oz. multilayer container. Inthe first step a three-layer preform insert was produced by acoextrusion blow molding process using an apparatus comprising a 1½″screw diameter Arburg press and a 15 mm screw diameter BOY 15 press(from Boy Machines Corporation, Exton, Pennsylvania) connected to amultilayer flow combining head with a circular nozzle which delivered a½ inch diameter tubular parison to a single cavity mold. The mold wasclosed on the parison to pinch off both ends of the parison. The parisonwas then inflated to form an insert. The multi-layer insert was trimmedto a length of 3⅜ inches and a diameter of 0.68 inches in the sectiondestined for the bottle wall. The three layers were of generally equalthickness such that COTBPR central layer was about 0.008 and locatedsubstantially centrally in the 0.025 inch wall thickness. The inner andouter layer of the three layer insert consisted of T98 PET bottle resin,modified with 10 percent isophthalic acid, supplied by Hoechst Trevira.The COTBPR resin had a melt viscosity of 5,680 poise at 270° C. Thethree layer insert was placed in an Arburg molding press and overmoldedwith an 0.14 inch layer of injected 86H PET bottle resin (available fromHoechst Trevira) to form a preform. The preform was then stretch blowmolded in a Sidel multi-station stretch blow molding machine to form a12 oz. container having a uniform COTBPR layer throughout the polyesterwalls and having good transparency. The COTBPR layer thickness in thewall area measured 0.0013 inches as compared to the 0.008 inch thicknessin the original insert from which it was formed. These thicknessmeasurements indicated a total area draw ratio of 6.67 for thestretchable COTBPR in the container.

Example 5

Thermoforming Followed by Stretch Blow Molding:

Multilayer sheets from Example 3 having 10 mil PETIP polyester on eitherside of a 5 mil thick central COTBPR layer were cut in 7 by 7 inchpieces. These multilayer sheets were then thermoformed at 145° C. toform an insert. Average insert thickness after thermoforming was 20.16mils indicating an average draw ratio of 1.24. The inserts were placedover the core of an injection molding machine and overmolded withpolyester bottle resin Polyclear® N10 (available from Hoechst Trevira),modified with 10 weight percent naphthalene dicarboxylic acid. In theovermolding step, molten N10 resin was injected onto the outer surfaceof the three layer thermoformed insert, to form a four layer preformhaving the structure N10/PETIP/COTBPR/PETIP. The preforms were thenreheated up to 145° C. and stretch blowmolded into a 500 ml wide mouthcontainer having a uniform COTBPR layer without fractures or tearsthroughout the wall section and good transparency. The COTBPR layerthickness in the wall area measured 0.45 mi. This thickness measurementindicates a total area draw ratio of 11.1 for the COTBPR layer in thecontainer.

What is claimed is:
 1. A multilayer laminate comprising (a) at least onelayer of wholly aromatic liquid crystalline polymer which is stretchableat a temperature below 200° C., and (b) at least one layer of non-liquidcrystalline polyester, wherein said multilayer laminate was stretched toat least 100 percent elongation while at a temperature below 200° C. andbelow the temperature of the molten state of said layer (a) of whollyaromatic liquid crystalline polymer so as to achieve molecularorientation in layer (b).
 2. The multilayer laminate of claim 1 whereinsaid stretched wholly aromatic liquid crystalline polymer layer (a) is apolyester and has repeat units corresponding to the formula:-[P¹]_(m)-[P²]_(n)-[P³]_(q)- wherein P¹, P² and P³ represent residues ofmonomeric moieties, with P¹ being an aromatic hydroxy carboxylic acid,p² being an aromatic dicarboxylic acid, and P³ being a phenoliccompound; and m, n and q represent mole percent of the respectivemonomers with m, n, and q being about 5-40 percent individually.
 3. Themultilayer laminate of claim 2, wherein said stretched wholly aromaticliquid crystalline polymer layer (a) additionally contains repeat unitsof monomeric moieties [P⁴]_(r), and [P⁵]_(s), where [P⁴]_(r) is a secondaromatic hydroxy carboxylic acid moiety different from P¹, and [P⁵]_(s)is a phenolic moiety different from P³, with r and s representing themole percent of the respective monomers, r being about 5-30 molepercent, and s being about 5-20 mole percent.
 4. The multilayer laminateof claim 3, wherein P¹ is 4-hydroxybenzoic acid, P² is terephthalicacid, P³ is 4,4′-dihydroxybiphenyl, P⁴ is 6-hydroxy-2-naphthoic acid,and P⁵ is resorcinol; and m is 5 to 40, n is 5 to 40, q is 5 to 40, r is5 to 30, and s is 5 to. 10 percent.
 5. The multilayer laminate of claim3, wherein P¹ is 4-hydroxybenzoic acid, P² is terephthalic acid, P³ is4,4′-dihydroxybiphenyl, P⁴ is 6-hydroxy-2-naphthoic acid, and P⁵ isresorcinol; and m is 30, n is 20, q is 10, r is 30, and s is 10 percent.6. The multilayer laminate of claim 1, wherein said layer of non-liquidcrystalline polyester (b) comprises monomeric residues selected from thegroup consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, ethyleneglycol, propylene glycol, and butylene glycolmoieties, and mixtures thereof.
 7. The multilayer laminate of claim 1,wherein said layer of non-liquid crystalline polyester (b) is selectedfrom the group consisting of polyethyleneterephthalate;polyethyleneisophthalate; polyethylene-2,6-naphthalate;polybutyleneterephthalate; polypropyleneterephthalate; post consumerrecycled polyethylene terephthalate; copolyesters where the diacidcomponent is terephthalic acid and derivatives thereof, isophthalic acidand derivatives thereof, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-,2,4-, 2,5-, 2,6-, 2,7, 2,8- isomers of naphthalene dicarboxylic acid andderivatives thereof, 4,4′-biphenyl dicarboxylic acid and derivativesthereof, 4,4′-diphenylether dicarboxylic acid and derivatives thereof,stilbenedicarboxylic acid and derivatives thereof, linear and mono andbis cyclic aliphatic dicarboxylic acids of 5-12 carbon atoms andderivatives thereof; copolyesters where the diol component is a linearaliphatic diol of 2-12 carbon atoms and derivatives thereof,2-methyl-propanediol, 2,2′-dimethylpropanediol, cyclohexanediol,cyclohexanedimethanol, 1,3-bis(2-hydroxyethoxy)benzene and derivativesthereof, 1,4-bis(2-hydroxyethoxy)benzene and derivatives thereof,bis(4-beta-hydroxyethoxyphenyl)sulfone and derivatives thereof,diethyleneglycol, poly(ethylene) glycol, poly(propylene) glycol,poly(tetramethylene) glycol, glycerol and derivatives thereof,trimethylolpropane and derivatives thereof, triethylolpropane andderivatives thereof, pentaerythritol and derivatives thereof; andcombinations and blends thereof.
 8. The multilayer laminate of claim 1,wherein said wholly aromatic liquid crystalline polymer layer (a) andsaid non-liquid crystalline polyester layer (b) are coextruded to formthe multilayer laminate, and subsequently are stretched while at atemperature below 200° C. and below that of the molten temperature of(a) to at least 100 percent elongation.
 9. The multilayer laminate ofclaim 8, wherein said coextruded laminate was subsequently expanded intoa mold with said stretching.
 10. The multilayer laminate of claim 8,wherein said coextruded laminate was subsequently blown to produce saidstretching.
 11. The multilayer laminate of claim 1, wherein saidlaminate has been stretched while at a temperature below 200° C. andbelow that of the molten temperature of (a) to at least 100 percentelongation by a method selected from the group consisting of uniaxialstretching, multiaxial stretching, and blowing into a mold.
 12. Themultilayer laminate of claim 1, wherein said laminate is in a formselected from the group consisting of planar, tubular, spiral wound, andplanar formed by the opening of a tubular laminate.
 13. The multilayerlaminate of claim 1, wherein said laminate following its formation isthermoformed into a shape.
 14. A container formed from the multilayerlaminate of claim 1 wherein said container is selected from the groupconsisting of a thermoformed container, an injection blow-moldedcontainer, an extrusion blow-molded container, and a stretch-blow moldedcontainer.
 15. A container formed from the multilayer laminate of claim1 wherein said container is selected from the group consisting of a bag,a pouch, and a tube.
 16. The container of claim 15 wherein saidcontainer is in the form of a tube and one or both ends have beenclosed.
 17. The container of claim 15 wherein the container is formed byfolding over and sealing a planar laminate to form a tube and closingone or more ends of the tube.
 18. A container formed from the multilayerlaminate of claim 1 wherein said container is selected from the groupconsisting of a box and a can.
 19. A container formed from themultilayer laminate of claim 1 wherein said stretched wholly aromaticliquid crystalline polymer layer (a) is a polyester and has repeat unitscorresponding to the formula: -[P¹]_(m)-[P²]_(n)-[P³]_(q)- wherein P¹,P² and P³ represent residues of monomeric moieties, with P¹ being anaromatic hydroxy carboxylic acid, P² being an aromatic dicarboxylicacid, and P³ being a phenolic compound; and m, n and q represent molepercent of the respective monomers with m, n, and q being about 5-40percent individually.
 20. A container formed from the multilayerlaminate of claim 19, wherein said stretched wholly aromatic liquidcrystalline polymer layer (a) additionally contains repeat units ofmonomeric moieties [P⁴]_(r) and [P⁵]_(s), where [P⁴]_(r) is a secondaromatic hydroxy carboxylic acid moiety different from P¹, and [P⁵]_(s)is a phenolic moiety different from P³, with r and s representing themole percent of the respective monomers, r being about 5-20 molepercent, and s being about 5-30 mole percent.
 21. The multilayercontainer of claim 20, wherein P¹ is 4-hydroxybenzoic acid, P² isterephthalic acid, P³ is 4,4′-dihydroxybiphenyl, P⁴ is6-hydroxy-2-naphthoic acid, and P³ is resorcinol; and m is 5 to 40, n is5 to 40, q is 5 to 40, r is 5 to 30, and s is 5 to 10 percent.
 22. Themultilayer container of claim 20, wherein P¹ is 4-hydroxybenzoic acid,P² is terephthalic acid, P³ is 4,4′-dihydroxybiphenyl, P⁴ is6-hydroxy-2-naphthoic acid, and P⁵ is resorcinol; and m is 30, n is 20,q is 10, r is 30, and s is 10 percent.
 23. A container formed from themultilayer laminate of claim 1, wherein said layer of non-liquidcrystalline polyester (b) comprises monomeric residues selected from thegroup consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, ethyleneglycol, propylene glycol, and butylene glycolmoieties, and mixtures thereof.
 24. A container formed from themultilayer laminate of claim 1, wherein said layer of non-liquidcrystalline polyester (b) is selected from the group consisting ofpolyethyleneterephthalate; polyethyleneisophthalate;polyethylene-2,6-naphthalate; polybutyleneterephthalate;polypropyleneterephthalate; post consumer recycled polyethyleneterephthalate; copolyesters where the diacid component is terephthalicacid and derivatives thereof, isophthalic acid and derivatives thereof,1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,4-, 2,5-, 2,6-, 2,7,2,8- isomers of naphthalene dicarboxylic acid and derivatives thereof,4,4′-biphenyl dicarboxylic acid and derivatives thereof,4,4′-diphenylether dicarboxylic acid and derivatives thereof,stilbenedicarboxylic acid and derivatives thereof, linear and mono andbis cyclic aliphatic dicarboxylic acids of 5-12 carbon atoms andderivatives thereof; copolyesters where the diol component is a linearaliphatic diol of 2-12 carbon atoms and derivatives thereof,2-methyl-propanediol, 2,2′-dimethylpropanediol, cyclohexanediol,cyclohexanedimethanol, 1,3-bis(2-hydroxyethoxy)benzene and derivativesthereof, 1,4-bis(2-hydroxyethoxy)benzene and derivatives thereof,bis(4-beta-hydroxyethoxyphenyl)sulfone and derivatives thereof,diethyleneglycol, poly(ethylene) glycol, poly(propylene) glycol,poly(tetramethylene) glycol, glycerol and derivatives thereof,triethylolpropane and derivatives thereof, triethylolpropane andderivatives thereof, pentaerythritol and derivatives thereof; andcombinations and blends thereof.
 25. A method for forming a multilayerlaminate comprising joining (a) at least one layer of a wholly aromaticliquid crystalline polymer which is stretchable at a temperature below200° C., and (b) at least one layer of a non-liquid crystallinepolyester to form a multilayer laminate, and stretching said multilayerlaminate to at least 100 percent elongation while at a temperature below200° C. and below the temperature of the molten state of layer (a) so asto achieve molecular orientation in layer (b).
 26. The method forforming a multilayer laminate according to claim 25 wherein saidstretching is conducted at a temperature above the glass transitiontemperature and below that of the molten state of said wholly aromaticliquid crystalline polymer.
 27. The method for forming a multilayerlaminate according to claim 26 wherein said stretching is conducted byexpansion in a mold.
 28. The method for forming a multilayer laminateaccording to claim 25 wherein said layers la) and (b) are formed andjoined by coextrusion.
 29. The method for forming a multilayer laminateaccording to claim 25 wherein said layers (a) and (b) are formed andjoined by injection molding.
 30. The method for forming a multilayerlaminate according to claim 25 wherein said laminate is stretched bythermoforming into a shape having an innermost surface and an outermostsurface, and further comprising the steps of placing said thermoformedmultilayer laminate into a mold, and injecting a thermoplastic materialinto said mold to form an outer layer of said injected thermoplasticmaterial in contact with said outermost surface of said thermoformedlaminate.
 31. A method for forming a multilayer laminate according toclaim 25 wherein said laminate initially is provided as a preform andsubsequently is expanded in a mold to produce said stretching.
 32. Amethod for forming a multilayer laminate according to claim 31 whereinsaid preform is biaxially stretched.
 33. A method for forming amultilayer laminate according to claim 25 wherein said wholly aromaticliquid crystalline polymer is a polyester and has repeat unitscorresponding to the formula: -[P¹]_(m)-[P²]_(n)-[P³]_(q)- wherein P¹,P² and P³ represent residues of monomeric moieties, with P¹ being anaromatic hydroxy carboxylic acid, P² being an aromatic dicarboxylicacid, and P³ being a phenolic compound; and m, n and q represent molepercent of the respective monomers with m, n, and q being about 5-40percent individually.
 34. A method for forming a multilayer laminateaccording to claim 33 wherein said wholly aromatic liquid crystallinepolyester additionally contains repeat units of monomeric moieties[P⁴]_(r) and [P⁵]_(s), where [P⁴]_(r) is a second aromatic hydroxycarboxylic acid moiety different from P¹, and [P⁵]_(s) is a phenolicmoiety different from P³, with r and s representing the mole percent ofthe respective monomers, r being about 5-30 mole percent, and s beingabout 5-20 mole percent.
 35. A method for forming a multilayer laminateaccording to claim 34, wherein P¹ is 4-hydroxybenzoic acid, P² isterephthalic acid, P³ is 4,4′-dihydroxybiphenyl, P⁴ is6-hydroxy-2-naphthoic acid, and P⁵ is resorcinol; and m is 5 to 40, n is5 to 40, q is 5 to 40, r is 5 to 30, and s is 5 to 10 percent.
 36. Amethod for forming a multilayer laminate according to claim 34 whereinP¹ is 4-hydroxybenzoic acid, P² is terephthalic acid, P³ is4,4′-dihydroxybiphenyl, P⁴ is 6-hydroxy-2-naphthoic acid, and P⁵ isresorcinol; and m is 30, n is 20, q is 10, r is 30, and s is 10 percent.37. A method for forming a multilayer laminate according to claim 25wherein said non-liquid crystalline polyester (b) comprises monomericresidues selected from the group consisting of terephthalic acid,isophthalic acid, naphthalene dicarboxylic acid, ethyleneglycol,propylene glycol, and butylene glycol moieties, and mixtures thereof.38. A method for forming a laminate according to claim 25 wherein saidnon-liquid crystalline polyester (b) is selected from the groupconsisting of polyethyleneterephthalate; polyethyleneisophthalate;polyethylene-2,6-naphthalate; polybutyleneterephthalate;polypropyleneterephthalate; post consumer recycled polyethyleneterephthalate; copolyesters where the diacid component is terephthalicacid and derivatives thereof, isophthalic acid and derivatives thereof,1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,4-, 2,5-, 2,6-, 2,7,2,8- isomers of naphthalene dicarboxylic acid and derivatives thereof,4,4′-biphenyl dicarboxylic acid and derivatives thereof,4,4′-diphenylether dicarboxylic acid and derivatives thereof,stilbenedicarboxylic acid and derivatives thereof, linear and mono andbis cyclic aliphatic dicarboxylic acids of 5-12 carbon atoms andderivatives thereof; copolyesters where the diol component is a linearaliphatic diol of 2-12 carbon atoms and derivatives thereof,2-methyl-propanediol, 2,2′-dimethylpropanediol, cyclohexanediol,cyclohexanedimethanol, 1,3-bis(2-hydroxyethoxy)benzene and derivativesthereof, 1,4-bis(2-hydroxyethoxy)benzene and derivatives thereof,bis(4-beta-hydroxyethoxyphenyl)sulfone and derivatives thereof,diethyleneglycol, poly(ethylene) glycol, poly(propylene) glycol,poly(tetramethylene) glycol, glycerol and derivatives thereof,trimethylolpropane and derivatives thereof, triethylolpropane andderivatives thereof, pentaerythritol and derivatives thereof; andcombinations and blends thereof.